Manufacturing process for porous material

ABSTRACT

A manufacturing process for a porous material is provided. The manufacturing process for a porous material includes the steps of: mixing a non-ionic surfactant with a precursor of a predetermined material to form a mixture comprising a continuous phase and a liquid crystalline mesophase comprising the non-ionic surfactants, wherein the precursor is essentially located in the continuous phase; coating or depositing the mixture onto a flexible substrate; and converting the precursor of the predetermined material.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.61/371,293, filed on Aug. 6, 2010, the entirety of which is incorporatedby reference herein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a manufacturing process for a porousmaterial, and in particular to a manufacturing process for a porousmaterial using surfactants as the pore former incorporated withcontinuous roll-to-roll processes.

2. Description of the Related Art

Generally, porous materials are materials with porous structures.According to the International Union of Pure and Applied Chemistry(IUPAC), porous materials can be divided into three types, such asmicroporous, mesoporous, and macroporous materials. The microporousmaterials comprise pores of diameters substantially less than 2 nm, themacroporous materials comprise pores of diameters substantially greaterthan 50 nm, and the mesoporous materials comprise pores of diametersamong 2-50 nm.

Surfactants typically comprise organic amphiphilic molecules havinghydrophilic and hydrophobic groups and can be dissolved in organicsolutions and aqueous solutions. When the surfactant concentration inwater is low, molecules of the surfactant will be located at theinterface between air and water. When the surfactant concentration isincreased to a critical micelle concentration (CMC), the surfactantswill aggregate to be the micelles. The hydrophilic group of surfactantin micelle will face outward to reduce a contact area between the watermolecules and the hydrophobic groups.

A hydrophilic-lipophilic balance (HLB) of a surfactant is thehydrophilic degree of the surfactants. A surfactant with higher HLBvalue has higher hydrophilicity. For example, surfactants with HLBvalues of 8 or higher have high water solubility.

Since the solution concentration is greater than the critical micelleconcentration, surfactant molecules will aggregate to form the micelle.Although the micelle is typically formed in a spherical shape, the sizeand shape of the micelle can be gradually changed in accordance withvariations in concentration and temperature. In addition, the size andshape of the micelle are also influenced by the chemical structure andmolecular weight of the surfactant. Based on formation conditions andcompositions, liquid crystals comprise thermotropic liquid crystals andlyotropic liquid crystals. The thermotropic liquid crystals are formeddue to temperature variations, and the lyotropic liquid crystals areformed due to concentration variations.

Based on the organization of molecules or surfactant aggregates, liquidcrystals comprise a smectic and nematic mesophase. In the nematic phase,all molecules or surfactant aggregates are aligned approximatelyparallel to each other with only a one-dimensional (orientational)order. In the smectic phase, all molecules or surfactant aggregatesexhibit both (two-dimensional) positional and orientational order.

In the prior art, one of the manufacturing processes for orderedmesoporous materials uses various surfactants as structure-directingagents or so-called templates. The surfactants can be, for examples,triblock copolymers, diblock copolymers or ionic surfactants. The abovemethod also uses alkoxides as a precursor to synthesize metal oxides orhydroxides by a sol-gel technique. Alternatively, the above method mayuse carbonaceous monomers or oligomers as precursors of carbons to mixwith surfactants and then the surfactants are removed as the surfactantsare arranged orderly and the precursors are polymerized. The obtainedpolymers are then carbonized at a high temperature such that highlyordered mesoporous carbons are obtained. However, the research to dateabout formation of the mesoporous materials mainly focuses on changingthe synthesis conditions of the precursors or the materials. Forexample, U.S. Pat. Nos. 5,057,296, 5,108,725, 5,102,643 and 5,098,684disclose using ionic surfactants as a template for manufacturing porousmaterials, wherein pore sizes thereof are greater than 5 nm. However,the formed mesoporous structures are not stable.

The conventional manufacturing processes for highly ordered mesoporousmaterials are typically by template-directed synthesis. The methodsthereof can be divided into hard template methods and soft templatemethods according to features and restrictions of the template usedtherein. Since Kresge et al. disclosed a synthesis method for formingmesoporous silica in 1992 (C. T. Kresge, M. E. Leonowicz, W. J. Roth, J.C. Vartuli, and J. S. Beck, “Ordered mesoporous molecular sievessynthesized by a liquid-crystal template mechanism” Nature, vol 359, no.6397, pp. 710-712, 1992), research about manufacturing mesoporousmaterials by template methods have been developed in the last decade.More precisely, research about manufacturing mesoporous materials bytemplate methods that mainly focus on selections of surfactant and theconditions of material synthesizing has been carried out. For the softtemplate method, through selecting the surfactants and adjusting thesynthesis conditions, the surfactants as a structure-directing agentwill self-assemble into a highly ordered liquid crystalline phase whilethe concentration of the surfactant is greater than the critical micelleconcentration, thereby forming various types of highly orderedmesoporous channels such as MCM-41, SBA-15 and MCM-50 having atwo-dimensional high symmetry, and KIT-5, SBA-16, SBA-11, SBA-2, MCM-48,etc. having a three-dimensional high symmetry. For the hard templatemethod, a previously prepared mesoporous silicon dioxide, such asSBA-15, is used as a template to prepare reversed mesoporous materials.After mixing carbon precursors with SBA-15, the carbon precursors areconverted to carbon. The silicon dioxide in the obtained product isremoved by using hydrofluoric acid or strong bases and then the orderedmesoporous carbon named as CMK-3 is obtained. Although highly orderedmesoporous materials having microstructures can also be obtained, thecost of the hard template method is high and the structures of theobtained materials are reversed mesoporous structures.

The highly ordered mesoporous materials synthesized by using surfactantsas structure-directing agents have characteristics such as high specificsurface areas, uniform and adjustable pore sizes, and regular porechannel arrangements such that high value in applications such asseparation, catalyst, electromagnetic materials, and chemical sensingcan be seen, wherein the representative materials are mesoporous silicondioxides.

In the prior art, the metal hydroxide or metal oxide are obtained by aprecipitation, hydrolysis, condensation and redox reaction in batchprocess. In a batch process, the concentration gradient of reactantexists. Therefore, it is hard to control the uniformity of conversion.With a scale-up design in a conventional batch process, there aredisadvantages of poor reaction uniformity and unstable quality.

BRIEF SUMMARY OF THE INVENTION

In one embodiment of the present invention, a continuous process formanufacturing a porous material is provided. The manufacturing processfor a porous material includes the steps of: mixing a non-ionicsurfactant with a precursor of a predetermined material to form amixture comprising a continuous phase and a liquid crystalline mesophasecomprising the non-ionic surfactants, wherein the precursor isessentially located in the continuous phase; coating or depositing themixture onto a flexible substrate; and converting the precursor of thepredetermined material.

In one embodiment of the present invention, the continuous processfurther includes coating or depositing a base onto a layer comprisingthe precursor of the predetermined material.

In another embodiment of the present invention, the continuous processfurther includes coating or depositing a base precursor or a mixture ofa base and a fugitive acid onto a layer comprising the precursor of thepredetermined material.

In a further embodiment of the present invention, the continuous processfurther includes adding a base precursor or a mixture of a base and afugitive acid into the mixture.

Preferably, the liquid crystalline mesophase is a smectic phase or asmectic hexagonal phase. The liquid crystalline mesophase is the form ofa column having a diameter from about 2 nm to about 20 nm.

Preferably, the non-ionic surfactants have the HLB value from 5 to 24.More preferably, the non-ionic surfactants have the HLB value from 10 to14.

The mixture comprises two continuous phases, or a continuous liquidcrystalline mesophase and a continuous non-liquid crystalline phase.

In further another embodiment of the present invention, the continuousprocess further includes coating or depositing the mixture onto theflexible substrate in a roll-to-roll manner.

Preferably, the flexible substrate comprises a metal or polymer.

In an embodiment of the present invention, the continuous processfurther includes heating or drying, after converting the precursor ofthe predetermined material, and removing the surfactants, whereinremoving the surfactants comprises washing the surfactants by a solventor a solvent mixture.

The precursor is converted to obtain the predetermined material byprecipitation, hydrolysis, condensation, redox reaction, polymerization,or crosslinking.

The mixture is coated or deposited onto the flexible substrate bycasting, impregnation, spraying, dipping, gravure, doctor blade, slot,slit, curtain, reverse or transfer coating, or printing.

The predetermined material is selected from the group consisting ofsilicon dioxide, titanium dioxide, nickel hydroxide, nickel oxide, andmanganese oxide.

The precursor includes tetraethoxysilane, titanium salt, organotitanium,titanium alkyoxide, nickel salt, organonickel complex, manganese salt,organomanganese complex, or combinations thereof.

Preferably, the non-ionic surfactants comprise a block, graft, or branchcopolymer.

More preferably, the non-ionic surfactants comprise ethylene oxide (EO)copolymer, propylene oxide (PO) copolymer, butylene oxide copolymer,vinyl pyridine copolymer, vinyl pyrrolidone, epichlorohydrin copolymer,styrene copolymer, acrylic copolymer, or combinations thereof.

Alternatively, the non-ionic surfactants comprise polyoxyethylenealkylether having a chemical formula of C_(x)H_(2x+1)( EO)_(y)H, whereEO represents an ethylene oxide, x is not less than 12, and y is notless than 6.

Preferably, the molecular weight of the non-ionic surfactants is between500 and 20000. More preferably, the molecular weight of the non-ionicsurfactants is between 600 and 10000.

In an embodiment of the present invention, the continuous processfurther includes adding a swelling agent into the mixture.

In another embodiment of the present invention, a process formanufacturing a porous material includes the steps of: mixing anon-ionic surfactant with a precursor of a predetermined material andeither a base precursor or a first mixture of a base and a fugitive acidto form a second mixture comprising a continuous phase and a liquidcrystalline mesophase comprising the non-ionic surfactants, wherein theprecursor is essentially located in the continuous phase; coating ordepositing the second mixture onto a flexible substrate; heating orilluminating the base precursor or the first mixture of the base and thefugitive acid; and converting the precursor of the predeterminedmaterial.

Preferably, the base precursor or the mixture of the base and thefugitive acid is a nitrogen-containing compound, guanidine, urea, amine,imine, or derivatives thereof. The base precursor or the mixture of thebase and the fugitive acid is heated under a temperature ranging from30° C. to 150° C.

In further another embodiment of the present invention, a process formanufacturing a porous material includes the steps of: mixing anon-ionic surfactant with a precursor of a predetermined material toform a mixture comprising a continuous phase and a liquid crystallinemesophase comprising the non-ionic surfactants, wherein the precursor isessentially located in the continuous phase; coating or depositing themixture onto a flexible substrate; coating or depositing a baseprecursor or a mixture of a base and a fugitive acid onto a layercomprising the precursor of the predetermined material; heating orilluminating the base precursor or the mixture of the base and thefugitive acid; and converting the precursor of the predeterminedmaterial.

In one embodiment of the present invention, a continuous process formanufacturing an electrode includes the steps of mixing a non-ionicsurfactant with a precursor of a predetermined material to form amixture comprising a continuous phase and a liquid crystalline mesophasecomprising the non-ionic surfactants, wherein the precursor isessentially located in the continuous phase; coating or depositing themixture onto a metal substrate; and converting the precursor of thepredetermined material.

In another embodiment of the present invention, a continuous process formanufacturing porous material includes the steps of: mixing a surfactantwith a nickel salt or organonickel complex to form a mixture; adding asilver halide and a developing agent or reducing agent into the mixture;coating or depositing the mixture onto a flexible substrate; reactingthe silver halide with the developing agent or reducing agent underillumination; and converting the nickel salt or organonickel complex toobtain nickel hydroxide.

In a further embodiment of the present invention, a continuous processfor manufacturing an electrode includes the steps of: mixing asurfactant with a nickel salt or organonickel complex to form a mixture;adding a silver halide and a developing agent or reducing agent into themixture; coating or depositing the mixture onto a metal substrate;reacting the silver halide with developing agent or reducing agent underillumination; and converting nickel salt or organonickel complex toobtain nickel hydroxide.

Preferably the developing agent or reducing agent comprises an organiccompound, hydroquinone, aminophenol, phenylene diamine, derivativesthereof, or combinations thereof. More preferably, the developing agentor reducing agent comprises methyl p-aminophenol, N-methyl-p-aminophenolsalt, 1-phenyl-3-pyrazolidinone, derivatives thereof, or combinationsthereof.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention can be more fully understood by reading thesubsequent detailed description and examples with references made to theaccompanying drawings, where:

FIG. 1 is a flow chart of a manufacturing process for porous materialsof the invention;

FIGS. 2 a, 2 b and 2 c are schematic diagrams showing a continuousroll-to-roll coating process of the invention, respectively;

FIGS. 3 a and 3 b are schematic diagrams showing a continuousroll-to-roll removing, drying, and scraping steps of the invention,respectively;

FIG. 4 is a schematic diagram showing a continuous roll-to-rollelectrode cutting step of the invention;

FIGS. 5 a, 5 b, 5 c, 5 d, and 5 e are schematic diagrams showing aroll-to-roll manufacturing process for silver-containing porousmaterials of the invention;

FIG. 6 a is a plot for the isotherm of the porous nickel hydroxide ofExample 1;

FIG. 6 b is a plot for the pore size distribution of the porous nickelhydroxide of Example 1;

FIG. 7 a is a plot for the isotherm of the porous nickel hydroxide ofExample 2; and

FIG. 7 b is a plot for the pore size distribution of the porous nickelhydroxide of Example 2.

DETAILED DESCRIPTION OF THE INVENTION

The following description is made for the purpose of illustrating thegeneral principles of the invention and should not be taken in alimiting sense.

Manufacturing of Porous Materials

Synthesis methods capable of mass production are provided to synthesizethe porous materials using the surfactants as the pore former. Accordingto the present invention, the continuous process for manufacturing aporous material includes the steps of mixing a non-ionic surfactant witha precursor of the predetermined material to obtain a mixture andcoating or depositing the mixture onto the flexible substrate in a rollto roll manner. Next, conversion is performed to obtain a composite sol.After removing the non-ionic surfactants and residue ions, the porousmaterial is obtained. In addition, depending on the porous materials, aheating treatment may optionally be performed to conduct a dehydrationor phase transformation after the drying step.

In a batch process, the concentration gradient of reactant is existedsuch that it is hard to control the uniformity of the conversion.According to embodiments of the invention, diffusion distances ofreactant can be controlled with an adjustable film thickness in theconverting step to achieve uniform conversions in the continuous massproduction.

FIG. 1 is a flow chart showing an exemplary continuous process formanufacturing a porous material. As shown in FIG. 1, in a mixing stepS1, raw materials such as at least one non-ionic surfactant and aprecursor of a predetermined material are mixed to obtain a mixture. Themixture comprises a continuous phase and a liquid crystalline mesophasecomprising the non-ionic surfactants. The precursor is essentiallylocated in the continuous phase, wherein the mixture comprises twocontinuous phases, or a continuous liquid crystalline mesophase and acontinuous non-liquid crystalline phase.

Preferably, the liquid crystalline mesophase is a smectic phase. Morepreferably, the liquid crystalline mesophase is a smectic hexagonalphase. A column of a smectic hexagonal phase has a diameter from about 2nm to about 20 nm.

In a coating or depositing step S2, as shown in FIG. 2, the mixture iscoated or deposited onto a flexible substrate (e.g., a substrate 200 asshown in FIGS. 2 a˜2 c) during a continuous process (e.g., performed bya coater 202 as shown in FIGS. 2 a˜2 c). The flexible substrate can bemetal or polymer. After the coating or depositing step, the precursor ofthe predetermined material is located in the continuous phase comprisingthe non-ionic surfactants and can be converted to the predeterminedmaterial. Methods for the conversion way can be precipitation,hydrolysis, condensation, redox reaction, polymerization, crosslinkingor combinations thereof. In the coating or depositing step S2, themixture is coated or deposited onto the flexible substrate to obtain thefilm (e.g., a film 204) by casting, impregnation, spraying, dipping,gravure, doctor blade, slot, slit, curtain, reverse or transfer coating,or printing .

Conversion uniformity can be controlled by adjusting the film thicknessand diffusion distance of reactant in a continuous process. Furthermore,when a base precursor or the mixture of a base and a fugitive acid isadded into the mixture, the hydroxyl ion concentration can be controlledby heating or illuminating. Because a base precursor or the mixture of abase and a fugitive acid and precursor can be well mixed before theconverting step, the conversion uniformity can be controlled both for abatch or a continuous process.

The predetermined material can be oxide or hydroxide, such as silicondioxide, titanium dioxide, nickel hydroxide, nickel oxide, manganeseoxide and combinations thereof. For example, if the predeterminedmaterial is silicon dioxide, tetraethoxysilane (TEOS) can be used asprecursors. If the predetermined material is titanium dioxide, titaniumsalt, organotitanium complexes or titanium alkoxide can be used asprecursors. If the predetermined material is nickel hydroxide or nickeloxide, nickel salts or organonickel complexes can be used as precursors.If the predetermined material is manganese oxide (MnO_(x)),organomanganese complexes, manganese salts such as potassiumpermanganate and manganese sulfate, or potassium permanganate andmanganese acetate can be used as precursors.

The non-ionic surfactants can be block, graft or branch copolymers. Inaddition, the non-ionic surfactants can be selected from the groupconsisting of ethylene oxide (EO) copolymer, propylene oxide (PO)copolymer, butylene oxide copolymer, vinyl pyridine copolymer, vinylpyrrolidone, epichlorohydrin copolymer, styrene copolymer, acryliccopolymer, and combinations thereof. Further, the non-ionic surfactantsmay include the polyoxyethylene alkylether, such asC_(x)H_(2x+1)EO_(y)H, where x is not less than 12 and y is not less than6.

Preferably, the molecular weight of the non-ionic surfactant is between500 and 20000. More preferably, the molecular weight of the non-ionicsurfactant is between 600 and 10000.

Preferably, the non-ionic surfactants may have an HLB value from 5 to24. More preferably, the non-ionic surfactants may have an HLB valuefrom 10 to 14.

Precipitation refers to at least one kind of metal ions being convertedto obtain the undissolvable material. For example, Co(OH)₂ can beobtained by reacting the cobalt salt with hydroxyl ions. The hydroxylions can be produced from a base, base precursor or the mixture of thebase and the fugitive acid. For a base, hydroxyl ion concentrations canbe increased by dissolving a base into an aqueous solution. For example,sodium hydroxide and potassium hydroxide are the commonly used base. Fora base precursor or the mixture of a base and a fugitive acid, thehydroxyl ion concentration is gradually increased by heating orilluminating, and the reaction rate can be controlled when the baseprecursor or the mixture of the base and the fugitive acid isdecomposed. The base precursor or the mixture of the base and thefugitive acid can be the nitrogen-containing compound, such asguanidine, urea, amine, imine or derivatives thereof.

As shown in FIG. 1, after the coating or depositing step S2, theflexible substrate is conveyed to the next station by a continuousroll-to-roll process (e.g., a process performed by a roll-to-roll typeconveyer 222 shown in FIGS. 2 a, 2 b and 2 c).

After the mixture containing precursor and non-ionic surfactants arecoated or deposited onto flexible substrate as shown in as FIG. 2 a, aconverting step S3, as shown in FIG. 1, is applied to convert theprecursor to the predetermined material. In another embodiment, afterthe mixture is coated or deposited onto a flexible substrate (e.g. thesubstrate 200) to form a film (e.g. the film 204), a base, baseprecursor or the mixture of the base and the fugitive acid can be coatedor deposited onto a flexible substrate. The method of coating ordepositing can be a dipping, spraying (refer to the sprayer 206 in FIG.2 b), coating (refer to the coater 208 in FIG. 2 c), attaching, casting,impregnation, gravure, doctor blade, slot, slit, curtain, reverse, orprinting, thereby obtaining the predetermined materials. When a baseprecursor or the mixture of the base and the fugitive acid is used as areactant, a heating or illuminating treatment step (not shown) isrequired in the converting step S3 to obtain the predetermined material.

As shown in FIG. 2 a, the base precursor or the mixture of the base andthe fugitive acid as a reactant, can be mixed in the mixture obtained atthe step S1.

As shown in FIG. 1, after the converting step S3, a removing step S4 isperformed to remove the non-ionic surfactants and residue ions in thecomposite sol over the flexible substrate, wherein the composite solcontains the predetermined material, non-ionic surfactants and residueions. After removing the non-ionic surfactants and residue ions, porousmaterials are obtained. In preferred embodiments, water or suitablesolvents can be used for removing the non-ionic surfactants and residueions. In the removing step S4, a spray washing (e.g. by a sprayer 310)can be directly performed on the substrate to obtain the porous materialas shown in FIG. 3 a. After the removing step S4, the porous materialsare dried (e.g. by a dryer 312), scraped (e.g. by a scraper 314) andcollected. In another embodiment, after the converting step S3, thecomposite sol is scraped (e.g. by a scraper 314) into a washing tank(e.g. by a tank 316) to remove non-ionic surfactants and residue ions,as shown in FIG. 3 b.

As shown in FIG. 1, after removing non-ionic surfactants and residueions in step S4, a drying step S5 is then performed by a spray drying,freeze drying, or continuous tunnel drying or by using a batch oven toremove the solvent or the water, as shown in FIGS. 3 a and 3 b.

As shown in FIG. 1, a heating treatment S6 may optionally be performedafter the drying step S5 to conduct a dehydration or phasetransformation. For example, the TiO₂ crystalline phase can be changedfrom anatase to rutile after a heating treatment.

The process of the invention can be synthesized by using the surfactantsas the pore former and is not limited to only synthesizing the specificmaterials, porous metal oxide, hydroxides, or the like.

In the preferred embodiment of the invention, tetraethoxysilane (TEOS)is used as the precursor to be incorporated with a non-ionic surfactant,such as P123 (a triblock copolymer produced by BASF® Corp.) orC₁₆H₃₃EO₁₀H for obtaining SiO₂ by using a sol-gel method. After removalof P123 or C₁₆H₃₃EO₁₀H, porous SiO₂. A titanium salt or organotitainiumcomplex, such as titanium alkyoxide, can be used as precursors forobtaining TiO₂. For example, titanium isopropoxide or titanium butoxideis mixed with non-ionic surfactants and then coated or deposited onto aflexible substrate. After a converting step, a removing step isperformed to remove the non-ionic surfactants to obtain the porous TiO₂.

In order to enhance conductivity of the predetermined material, anadditive can be added into the mixture. The additive can be metal saltor a conductive agent. For example, cobalt salt or organocobaltcomplexes can be added into the mixture of the nickel salt ororganonickel complexes, C₁₆H₃₃EO₁₀H or P123 surfactants. After theconverting and removing steps, the porous material of the cobalt-dopednickel hydroxide can be obtained. In another embodiment, the conductiveagent, such as graphite, graphene, carbon black, carbon nanotube (CNT)or metal particles which comprises Ti, Pt, Ag, Au, Al, Ru, Fe, V, Ce,Zn, Sn, Si, W, Ni, Co, Mn, In, Os, Cu, or Nb can be added into themixture. The precursor is converted to the predetermined material, andthen a removing step is performed to obtain the composite with porousstructure.

Preferably, the manufacturing process further includes the steps ofadding a swelling agent into the mixture, wherein the swelling agent isselected from the group consisting of 1,3,5-trimethylbenzene (TMB),cholesterol, polystyrene, polyethers, polyetheramines, polyacrylate,polyacrylic and derivatives thereof.

Manufacturing Electrodes with Porous Materials

For the manufacturing of an electrode, a metal substrate made of nickel,copper, or aluminum can be applied. Without scraping the composite solfrom the metal substrate, the porous materials can be obtained on themetal substrate after the removing step of the non-ionic surfactants andresidue ions and the drying step. Electrodes comprising porous materialscan be manufactured by using an adequate cutting step (e.g. by thecutter 318 shown in FIG. 4) in a continuous process. The electrodes canbe applied to batteries, super capacitors or fuel cells.

In order to enhance conductivity of predetermined material, an additivecan be added into a mixture. The additive can be metal salt or aconductive agent. For example, the nickel salt or organonickelcomplexes, C₁₆H₃₃EO₁₀H or P123 surfactants and cobalt salt ororganocobalt complexes are mixed to obtain a mixture and coated ordeposited onto a metal substrate. After the converting and removingsteps, the porous material of the cobalt doped nickel hydroxide on themetal substrate can be obtained. In another embodiment, the conductiveagent, such as graphite, graphene, carbon black, carbon nanotube (CNT)or metal particles which comprises Ti, Pt, Ag, Au, Al, Ru, Fe, V, Ce,Zn, Sn, Si, W, Ni, Co, Mn, In, Os, Cu, or Nb can be added into themixture. The mixture is converted to the composite sol. After a step ofremoving the non-ionic surfactants and residue ions and a step ofdrying, electrodes with porous material can be obtained by an adequatecutting step.

Manufacturing Electrodes with Porous Materials Containing SilverParticles

In order to increase the conductivity of predetermined materials, silverhalide, such as silver chloride, silver bromide, and silver iodide, anda developing agent or reducing agent can be added into the mixture.During manufacturing of the electrodes, silver halide is reduced tosilver particles in the porous materials. Under illumination (e.g. bythe illumination device 520 shown in FIG. 5 a), few silver ions will bereduced to silver atoms as the nuclei. In the existence of silver atoms,a developing agent or reducing agent can be used to reduce the residuesilver ions to silver particles. Typically, the developing agent orreducing agent is an organic compound including hydroquinone,aminophenol, phenylene-diamine, derivatives thereof, and combinationsthereof. Preferably, the developing agent or reducing agent can bemethyl p-aminophenol, N-methyl-p-aminophenol salt,1-phenyl-3-pyrazolidinone, derivatives thereof, and combinationsthereof.

In another embodiment, as shown in FIGS. 5 a-5 b, silver halide, such assilver chloride, silver bromide, and silver iodide, and a developingagent or reducing agent can be added into the mixture. A coating ordepositing step is performed after the mixing step. Before theconverting step, silver halide is reduced to silver particles byreacting with the developing agent or reducing agent under illumination(e.g. by illumination device 520 shown in FIGS. 5 a and 5 b). A base iscoated or deposited (e.g. by the sprayer 206 or the coater 208 shown inFIGS. 5 a and 5 b, respectively) onto a flexible substrate to convertthe precursor to Ni(OH)₂. The residue silver ions can be further reducedto silver particles under the basic condition. After the removing step(e.g. by a sprayer 310 as shown in FIG. 5 c) and drying step (e.g. by adryer 312 as shown in FIG. 5 c), a porous Ni(OH)₂ containing silverparticles is obtained as shown in FIGS. 5 c. In another embodiment shownin FIG. 5 d, the composite sol is scraped (e.g. by a scraper 314) into awashing tank (e.g. by a tank 316) to remove non-ionic surfactants andresidue ions. Then the porous Ni(OH)₂ containing silver particles isobtained after a drying step.

In another embodiment of the invention, silver halide, such as silverchloride, silver bromide, and silver iodide, and a developing agent orreducing agent can be added into the mixture. The mixture is coated ordeposited onto a metal substrate. The metal substrate can be nickel,copper, or aluminum. After the converting step, the composite sol is notscraped from the metal substrate. Electrodes with porous Ni(OH)₂containing silver particles can be obtained by a removing step and acutting step (e.g. by a cutting 318 as shown in FIG. 5 e). Theelectrodes can be applied to batteries, super capacitors or fuel cells.

The present invention provides two exemplary embodiments of themanufacturing of porous nickel hydroxide as follows.

EXAMPLE 1

A surfactant C₁₆H₃₃EO₁₀H, methanol, and nickel chloride are mixed inwater to form a mixture. The content of C₁₆H₃₃EO₁₀H in the mixture is 60wt. %. The mixture is deposited onto substrate to form a film withthickness of 4 mm. The converting step is conducted by spraying a NaOHsolution under 25° C. to obtain a Ni(OH)₂ composite sol. After washingby water and ethanol, a drying step is performed at 60° C. to obtain aporous nickel hydroxide. As shown in FIG. 6 a, the isotherm plot of thenickel hydroxide exhibits a capillary condensation step at relativepressure from 0.4 to 0.8 and exhibits the pores structure in the nickelhydroxide As shown in FIG. 6 b, the pore size distribution of the porousnickel hydroxide is narrow and the specific surface area and porediameter of the porous nickel hydroxide are 525.0 m²/g and approximately6.1 nm, respectively.

EXAMPLE 2

A surfactant C₁₆H₃₃EO₁₀H, urea, and nickel chloride are mixed in waterto form a mixture. The content of C₁₆H₃₃EO₁₀H in the mixture is 60 wt.%. The converting step is conducted by heating at 65° C. to obtain aNi(OH)₂ composite sol. After washing by water and ethanol, a drying stepis performed at 60° C. to obtain a porous nickel hydroxide. FIG. 7 ashows the isotherm of the porous nickel hydroxide of Example 2. As shownin FIG. 7 a, the isotherm plot of the nickel hydroxide exhibits acapillary condensation step at relative pressure from 0.4 to 0.8 andexhibits the pores structure in the nickel hydroxide. As shown in FIG. 7b, the pore size distribution of the porous nickel hydroxide is narrowand the specific surface area and pore diameter of the porous nickelhydroxide are 285.5 m²/g and approximately 3.8 nm, respectively.

While the invention has been described by way of example and in terms ofthe preferred embodiments, it is to be understood that the invention isnot limited to the disclosed embodiments. To the contrary, it isintended to cover various modifications and similar arrangements (aswould be apparent to those skilled in the art). Therefore, the scope ofthe appended claims should be accorded the broadest interpretation so asto encompass all such modifications and similar arrangements.

1. A continuous process for manufacturing a porous material, comprising:mixing a non-ionic surfactant with a precursor of a predeterminedmaterial to form a mixture comprising a continuous phase and a liquidcrystalline mesophase comprising the non-ionic surfactants, wherein theprecursor is essentially located in the continuous phase; coating ordepositing the mixture onto a flexible substrate; and converting theprecursor of the predetermined material.
 2. The continuous process ofclaim 1, further comprising coating or depositing a base onto a layercomprising the precursor of the predetermined material.
 3. Thecontinuous process of claim 1, further comprising adding a baseprecursor or a mixture of a base and a fugitive acid into the mixture.4. The continuous process of claim 1, wherein the liquid crystallinemesophase is a smectic phase or a smectic hexagonal phase.
 5. Thecontinuous process of claim 1, wherein the liquid crystalline mesophaseis the form of a column having a diameter from about 2 nm to about 20nm.
 6. The continuous process of claim 1, wherein the non-ionicsurfactants have an HLB value from 5 to
 24. 7. The continuous process ofclaim 6, wherein the non-ionic surfactants have the HLB value from 10 to14.
 8. The continuous process of claim 1, wherein the mixture comprisestwo continuous phases, or a continuous liquid crystalline mesophase anda continuous non-liquid crystalline phase.
 9. The continuous process ofclaim 1, further comprising coating or depositing the mixture onto theflexible substrate in a roll-to-roll manner.
 10. The continuous processof claim 1, wherein the flexible substrate comprises a metal or polymer.11. The continuous process of claim 1, further comprising heating ordrying after converting the precursor of the predetermined material. 12.The continuous process of claim 1, further comprising removing thesurfactants.
 13. The continuous process of claim 12, wherein removingthe surfactants comprises washing the surfactants by a solvent or asolvent mixture.
 14. The continuous process of claim 1, wherein theprecursor is converted to obtain the predetermined material byprecipitation, hydrolysis, condensation, redox reaction, polymerization,or crosslinking.
 15. The continuous process of claim 1, wherein themixture is coated or deposited onto the flexible substrate by casting,impregnation, spraying, dipping, attaching, gravure, doctor blade, slot,slit, curtain, reverse or transfer coating, or printing.
 16. Thecontinuous process of claim 1, wherein the predetermined material isselected from the group consisting of silicon dioxide, titanium dioxide,nickel hydroxide, nickel oxide, and manganese oxide.
 17. The continuousprocess of claim 1, wherein the precursor comprises tetraethoxysilane,titanium salt, organotitanium, titanium alkyoxide, nickel salt,organonickel complex, manganese salt, organomanganese complex, orcombinations thereof.
 18. The continuous process of claim 1, furthercomprising adding an additive, metal salt, conductive agent, carbonnano-tube, carbon black, graphite, graphene or metal particles into themixture.
 19. The continuous process of claim 1, wherein the non-ionicsurfactants comprises a block, graft, or branch copolymer.
 20. Thecontinuous process of claim 1, wherein the non-ionic surfactantscomprises ethylene oxide (EO) copolymer, propylene oxide (PO) copolymer,butylene oxide copolymer, vinyl pyridine copolymer, vinyl pyrrolidone,epichlorohydrin copolymer, styrene copolymer, acrylic copolymer, orcombinations thereof.
 21. The continuous process of claim 1, wherein thenon-ionic surfactants comprises polyoxyethylene alkylether having achemical formula of C_(x)H_(2x+1)(EO)_(y)H, where EO represents anethylene oxide, x is not less than 12, and y is not less than
 6. 22. Thecontinuous process of claim 1, wherein the molecular weight of thenon-ionic surfactants is between 500 and
 20000. 23. The continuousprocess of claim 22, wherein the molecular weight of the non-ionicsurfactants is between 600 and
 10000. 24. The continuous process ofclaim 1, further comprising adding a swelling agent into the mixture.25. The continuous process of claim 1, further comprising coating ordepositing a base precursor or a mixture of a base and a fugitive acidonto a layer comprising the precursor of the predetermined material. 26.The continuous process of claim 25, wherein the base precursor or themixture of the base and the fugitive acid is a nitrogen-containingcompound.
 27. The process of claim 25, wherein the base precursor or themixture of the base and the fugitive acid comprises guanidine, urea,amine, imine, or derivatives thereof.
 28. The continuous process ofclaim 25, wherein the base precursor or the mixture of the base and thefugitive acid is heated under a temperature ranging from 30° C. to 150°C.
 29. The continuous process of claim 28, wherein the base precursor orthe mixture of the base and the fugitive acid is heated under atemperature ranging from 30° C. to 70° C.
 30. A process formanufacturing a porous material, comprising: mixing a non-ionicsurfactant with a precursor of a predetermined material and either abase precursor or a first mixture of a base and a fugitive acid to forma second mixture comprising a continuous phase and a liquid crystallinemesophase comprising the non-ionic surfactants, wherein the precursor isessentially located in the continuous phase; coating or depositing thesecond mixture onto a flexible substrate; heating or illuminating thebase precursor or the first mixture of the base and the fugitive acid;and converting the precursor of the predetermined material.
 31. Acontinuous process for manufacturing a porous material, comprising:mixing a non-ionic surfactant with a precursor of a predeterminedmaterial to form a mixture comprising a continuous phase and a liquidcrystalline mesophase comprising the non-ionic surfactants, wherein theprecursor is essentially located in the continuous phase; coating ordepositing the mixture onto a flexible substrate; depositing a baseprecursor or a mixture of a base and a fugitive acid onto a layercomprising the precursor of the predetermined material; heating orilluminating the base precursor or the mixture of the base and thefugitive acid; and converting the precursor of the predeterminedmaterial.
 32. A continuous process for manufacturing an electrode,comprising: mixing a non-ionic surfactant with a precursor of apredetermined material to form a mixture comprising a continuous phaseand a liquid crystalline mesophase comprising the non-ionic surfactants,wherein the precursor is essentially located in the continuous phase;coating or depositing the mixture onto a metal substrate; and convertingthe precursor of the predetermined material.
 33. A continuous processfor manufacturing a porous material, comprising: mixing a surfactantwith a nickel salt or organonickel complex to form a mixture; adding asilver halide and a developing agent or reducing agent into the mixture;coating or depositing the mixture onto a flexible substrate; reactingthe silver halide with the developing agent or reducing agent underillumination; and converting the nickel salt or organonickel complex toobtain nickel hydroxide.
 34. The continuous process of claim 33, whereinthe developing agent or reducing agent comprises an organic compound.35. The continuous process of claim 33, wherein the developing agent orreducing agent comprises hydroquinone, aminophenol, phenylenediamine,derivatives thereof, or combinations thereof.
 36. The continuous processof claim 33, wherein the developing agent or reducing agent comprisesmethyl p-aminophenol, N-methyl-p-aminophenol salt,1-phenyl-3-pyrazolidinone, derivatives thereof, or combinations thereof.37. A continuous process for manufacturing an electrode, comprising:mixing a surfactant with a nickel salt or organonickel complex to form amixture; adding a silver halide and a developing agent or reducing agentinto the mixture; coating or depositing the mixture onto a metalsubstrate; reacting the silver halide with developing agent or reducingagent under illumination; and converting nickel salt or organonickelcomplex to obtain nickel hydroxide.